A series of novel block copolymers,
processable from single organic solvents and subsequently rendered
amphiphilic by thermolysis, have been synthesized using Grignard metathesis
(GRIM) and reversible addition–fragmentation chain transfer
(RAFT) polymerizations and azide–alkyne click chemistry. This
chemistry is simple and allows the fabrication of well-defined block
copolymers with controllable block lengths. The block copolymers,
designed for use as interfacial adhesive layers in organic photovoltaics
to enhance contact between the photoactive and hole transport layers,
comprise printable poly(3-hexylthiophene)-block-poly(neopentyl p-styrenesulfonate), P3HT-b-PNSS. Subsequently,
they are converted to P3HT-b-poly(p-styrenesulfonate), P3HT-b-PSS, following deposition
and thermal treatment at 150 °C. Grazing incidence small- and
wide-angle X-ray scattering (GISAXS/GIWAXS) revealed that thin films
of the amphiphilic block copolymers comprise lamellar nanodomains
of P3HT crystallites that can be pushed further apart by increasing
the PSS block lengths. The approach of using a thermally modifiable
block allows deposition of this copolymer from a single organic solvent
and subsequent conversion to an amphiphilic layer by nonchemical means,
particularly attractive to large scale roll-to-roll industrial printing
processes.
In the printing industry, the exploitation of triggerable materials that can have their surface properties altered on application of a post-deposition external stimulus has been crucial for the production of robust layers and patterns. To this end, herein, a series of clickable poly(R-alkyl p-styrene sulfonate) homopolymers, with systematically varied thermally-labile protecting groups, has been synthesised via reversible addition-fragmentation chain transfer (RAFT) polymerisation. The polymer range has been designed to offer varied post-deposition thermal treatment to switch them from hydrophobic to hydrophilic. Suitable RAFT conditions have been identified to produce well-defined homopolymers (Đ, M w /M n < 1.11 in all cases) at high monomer conversions (>80% for all but one monomer) with controllable molar mass. Poly(p-styrene sulfonate) with an isobutyl protecting group has been shown to be the most readily thermolysed polymer that remains stable at room temperature, and was thus investigated further by incorporation into a diblock copolymer, P3HT-b-PiBSS, by click chemistry. The strategy for preparation of thermal modifiable block copolymers exploiting R-protected p-styrene sulfonates and azide-alkyne click chemistry presented herein allows the design of new, roll-to-roll processable materials for potential application in the printing industry, particularly organic electronics.
The controlled synthesis of poly(neopentyl p-styrene sulfonate) (PNSS) using reversible addition-fragmentation chain transfer (RAFT) polymerisation has been studied under a wide range of experimental conditions. PNSS, can be used as an organic-soluble, thermally-labile
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